US20180022900A1 - Polyamide moulding composition and moulded article made from this moulding composition - Google Patents
Polyamide moulding composition and moulded article made from this moulding composition Download PDFInfo
- Publication number
- US20180022900A1 US20180022900A1 US15/546,373 US201515546373A US2018022900A1 US 20180022900 A1 US20180022900 A1 US 20180022900A1 US 201515546373 A US201515546373 A US 201515546373A US 2018022900 A1 US2018022900 A1 US 2018022900A1
- Authority
- US
- United States
- Prior art keywords
- moulding composition
- weight
- polyamide
- mol
- partially crystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R2201/00—Connectors or connections adapted for particular applications
- H01R2201/26—Connectors or connections adapted for particular applications for vehicles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R33/00—Coupling devices specially adapted for supporting apparatus and having one part acting as a holder providing support and electrical connection via a counterpart which is structurally associated with the apparatus, e.g. lamp holders; Separate parts thereof
Definitions
- the present invention refers to a polyamide moulding composition consisting of the following components:
- component b) and c) add up to 25 to 45% by weight and the entirety of components a) to d) add up to 100% by weight.
- the present invention refers to a moulded article producible from this moulding composition.
- Polyamide moulded articles are broadly used in the engineering field, in particular for electronic components as well as components in the automotive field. Due to the demand for moulded articles with a reduced weight but a high mechanical strength these articles are in general reinforced by fillers, in particular fibrous fillers.
- Such polyamides moulded articles are also used for lamp articles, like housings or lamp sockets. These can be used for headlights or rear lamps, in particular in the automotive field. For such articles it is important that they show a minimal fogging also at high temperatures which can occur in the surrounding of the lamp.
- WO 2013/026779 A1 describes polyamide composition for LED applications with improved mechanical properties.
- JP 2009-149763 A describes a low volatility polyamide composition with good mechanical properties and a low fogging.
- the polyamide moulding composition is preferably based on Nylon 6 and Nylon 66.
- polyamide moulding composition which consists of the following components:
- composition has the proviso that the component b) and c) add up to 25 to 45% by weight and the entirety of components a) to d) add up to 100% by weight.
- the inventive composition is characterized by a very low condensable outgasing (fogging) resulting in a haze of a maximum of 10%.
- the haze is measured by determining the haze on a glass plate after a thermal treatment of pellets of the polyamide moulding composition at 200° C. for a period of 8 hours.
- the moulding composition has a deflection temperature under load (HDT (A)) according to ISO 75 of at least 190° C., preferably of at least 200 C, and more preferably of at least 210° C.
- HDT (A) deflection temperature under load
- the moulding composition has preferably a condensable outgasing (fogging) resulting in a haze of a maximum of 7%, more preferably of 5%.
- the moulding composition comprises the partially crystalline polyamide a) in an amount of 50 to 69.95% by weight, more preferably 53 to 64.9% by weight.
- the partially crystalline polyamide a) has a melting point of at least 270° C., preferred of 275 to 350° C., more preferred of 280 to 340° C., most preferred of 280 to 330° C.
- the at least one diamine of the partially crystalline polyamide a) is preferably selected from the group of diamines consisting of 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 3,3′-dimethyl-1,5-pentanediamine 1,6-hexanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylene-diamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine and 1,14-tetradecanediamine and mixtures thereof.
- the at least one aromatic dicarboxylic acid of the partially crystalline polyamide a) is preferably selected from the group of aromatic dicarboxylic acids consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, whereupon the portion of isophthalic acid is at most 25 mol-%, preferably at most 20 mol-%, more preferably at most 16 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the at least one aromatic dicarboxylic acid of the partially crystalline polyamide is selected from the group of aromatic dicarboxylic acids consisting of terephthalic acid and isophthalic acid, whereupon the portion of isophthalic acid is at most 25 mol-%, preferably at most 20 mol-%, more preferably at most 16 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the relative viscosity (measured on a solution made of 0,5 g polyamide in 100 ml m-cresol at 20° C.) of the partially crystalline polyamide a) is 1.40 to 2.0, preferably 1.45 to 1.90, more preferably 1.48 to 1.80.
- the partially crystalline polyamide a) clearly is a polymer and is not an oligomer.
- the partially crystalline polyamide a) is selected from the group of partially crystalline polyamides containing as dicarboxylic acids only aromatic dicarboxylic acids, consisting of polyamides with a 4T-unit, polyamides with a 5T-unit, polyamides with a 6T-unit, polyamides with a 8T-unit, polyamides with a 10T-unit, PA 4T/6T, PA 4T/8T, PA 6T/8T, PA 4T/MPMDT, PA 4T/4I, PA 5T/5I, PA 6T/6I, PA 9T/MODT, PA 9T/9I, PA 10T, PA 10T/6T, PA 10T/6T/10I/6I, PA 12T, PA MPMDT/6T, PA 10T/10I, PA 12T/12I, PA 4T/6T/8T, PA 4T/6T/10T, PA 4T/8T/10T, PA6T/8T/10T, PA 4T/6T/MPMDT and mixtures or blends thereof.
- the partially crystalline polyamide a) is selected from the group of partially crystalline polyamides consisting of PA 6T/61, PA 9T/MODT, PA 10T, PA 10T/6T, PA 10T/6T/10I/6I, PA 12T, PA MPMDT/6T, PA 10T/10I and mixtures or blends thereof.
- the partially crystalline polyamide a) is selected from the group of partially crystalline polyamides consisting of PA 6T/6I, PA 10T/6T, PA 10T/6T/10I/6I and mixtures or blends thereof.
- the partially crystalline polyamide 6T/6I is made from hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of hexamethylenediamine of 50 mol-%, an amount of terephthalic acid of 25 to 40 mol-% and an amount of isophthalic acid of 10 to 25 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the partially crystalline polyamide 6T/6I is made from 50 mol-% hexamethylenediamine, 30 to 40 mol-% terephthalic acid and 10 to 20 mol-% isophthalic acid, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the partially crystalline polyamide 6T/6I is made from 50 mol-% hexamethylenediamine, 35 mol-% terephthalic acid and 15 mol-% isophthalic acid, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the melting point of this partially crystalline polyamide is 325° C.
- composition of polyamide 6T/6I with 50 mol-% hexamethylenediamine, 35 mol-% terephthalic acid and 15 mol-% isophthalic acid is equivalent to the description PA 6T/6I (70/30 mol-%).
- the partially crystalline polyamide 10T/6T is made from decanediamine, hexamethylenediamine and terephthalic acid with an amount of decanediamine of 20 to 47.5 mol-%, an amount of hexamethylenediamine of 2.5 to 30 mol-% and an amount of terephthalic acid of 50 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%.
- the partially crystalline polyamide 10T/6T is made from decanediamine, hexamethylenediamine and terephthalic acid with an amount of decanediamine of 30 to 45 mol-%, an amount of hexamethylenediamine of 5.0 to 20 mol-% and an amount of terephthalic acid of 50 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%.
- the partially crystalline polyamide 10T/6T is made from decanediamine, hexamethylenediamine and terephthalic acid with an amount of decanediamine of 35 to 42.5 mol-%, an amount of hexamethylenediamine of 7.5 to 15 mol-% and an amount of terephthalic acid of 50 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%.
- the partially crystalline polyamide 10T/6T is made from 42.5 mol-% decanediamine, 7.5 mol-% hexamethylenediamine and 50 mol-% terephthalic acid, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%.
- the melting point of this partially crystalline polyamide is 295° C.
- the partially crystalline polyamide 10T/6T/10I/6I is made from decanediamine, hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of decanediamine of 7.5 to 20 mol-%, an amount of hexamethylenediamine of 30 to 42.5 mol-%, an amount of terephthalic acid of 36 to 49.15 mol-% and an amount of isophthalic acid of 0.85 to 14 mol-%, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the partially crystalline polyamide 10T/6T/10I/6I is made from decanediamine, hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of decanediamine of 12.5 to 20 mol-%, an amount of hexamethylenediamine of 30 to 37.5 mol-%, an amount of terephthalic acid of 37.5 to 47.5 mol-% and an amount of isophthalic acid of 2.5 to 12.5 mol-%, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the partially crystalline polyamide 10T/6T/10I/6I is made from decanediamine, hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of decanediamine of 14 to 19 mol-%, an amount of hexamethylenediamine of 31 to 36 mol-%, an amount of terephthalic acid of 40 to 45 mol-% and an amount of isophthalic acid of 5.0 to 10 mol-%, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the partially crystalline polyamide 10T/6T/10I/6I is made from 16.65 mol-% decanediamine, 33.35 mol-% hexamethylenediamine, 43.2 mol-% terephthalic acid and 6.8 mol-% isophthalic acid, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- the melting point of this partially crystalline polyamide is 318° C.
- polyamide is a generic term, which comprises both homopolyamides and copolyamides.
- the abbreviated polyamide nomenclature conforms to the norm ISO 1874-1:2010.
- the diamine 2-methyl-1,5-pentanediamine is abbreviated as MPMD.
- the diamine 2-methyl-1,8-octanediamine is abbreviated as MOD.
- the at least one fibrous reinforcing agent are selected from glass fibres, preferably chopped glass fibres.
- the fibres reinforcing agent is preferably comprised in an amount of 5 to 15% by weight, more preferably in an amount of 7 to 12% by weight.
- the chopped glass fibres have a fibre length of 1 to 25 mm, preferably 1.5 to 20 mm, more preferably 2 to 12 mm, most preferably 2.5 to 8 mm.
- the chopped glass fibres have a diameter of 4 to 20 um, preferably 5 to 15 ⁇ m, more preferably 6 to 12 ⁇ m.
- chopped glass fibres with a round, oval, elliptical, angular or rectangular cross-section are used.
- the chopped glass fibres Preferably have a round cross-section.
- the chopped glass fibres are equipped with a suitable sizing system, e.g. on a silane basis.
- Glass fibres made of all types of glass such are as e. g. A-, C-, D-, E-, M-, S-, R-glass or any mixtures thereof, can be used.
- Glass fibres made of E-glass or glass fibres made of mixtures with E-glass or mixtures with E-glass fibres are preferred.
- the at least one non-sized filler has preferably a needle like or flaky shape.
- the longest dimension of the non-sized filler particle is at most 2500 ⁇ m, preferably at most 700 ⁇ m, more preferably 0.1 to 300 um.
- a longest dimension of the non-sized filler particle of at most 2500 ⁇ m is particularly common with filler particles having a flaky shape.
- the non-sized fillers are selected from the group consisting of milled glass fibres, milled carbon fibres, glass flakes, whiskers, wollastonite, mica, phyllosilicates and mixtures thereof. These non-sized fillers are in any case different from the fibres reinforcing agents according to b).
- the at least one non-sized filler is preferably comprised in an amount of 15 to 35% by weight, more preferably 20 to 33% by weight.
- non-sized fillers are selected from the group consisting of milled glass fibres, milled carbon fibres, glass flakes, wollastonite, mica and mixtures thereof. More preferably the non-sized fillers are selected from the group consisting of milled glass fibres, wollastonite, mica and mixtures thereof.
- Mica can be natural mica or synthetic mica, whereas synthetic mica is preferred.
- Whiskers are needle-like mono-crystals from metals, oxides, borides, carbides, nitrides, polytitanates, carbon etc. with mostly polygonal cross section, e. g. potassium titanate-, aluminium oxide-, silicium carbide-whisker. Whiskers can be produced by vapour deposition (VS-mechanism) or deposition from a three-phase-system (VLS-mechanism).
- VS-mechanism vapour deposition
- VLS-mechanism three-phase-system
- phyllosilicates also named layered silicates, e. g. serpentine, talcum, mica, vermiculite, illite, smectites, montmorillonites, kaolin (also named china clay), bentonites can be used.
- Preferred as phyllosilicates are mica, montmorillonites and kaolin. More preferred as phyllosilicates are mica and montmorillonites.
- the moulding composition comprises 32 to 44% by weight, more preferably 35 to 42% by weight of the components b) and c) in sum.
- the moulding composition comprises at least one additive which is selected from the group consisting of inorganic stabilisers, organic stabilisers, lubricants, colouring- and marking materials, inorganic pigments, organic pigments, IR absorbers, antistatic agents, antiblocking agents, crystal-growth inhibitors, nucleating agents, condensation catalysts, chain extenders, defoamers, chain-lengthening additives, conductivity additives, carbon black, graphite, carbon nanotubes, mould-release agents, separating agents, flame retardants, non-halogen-containing flame retardants, anti-dripping-agents, impact modifiers, optical brighteners, photochromic additives, metallic pigments, metal-coated particles, or mixtures thereof, preferably inorganic stabilizers as copper and potassium iodide.
- inorganic stabilisers organic stabilisers, lubricants, colouring- and marking materials
- inorganic pigments organic pigments
- IR absorbers antistatic agents, antiblocking agents, crystal-growth inhibitors, nucleating
- the at least one additive is preferably comprised in an amount of 0.05 to 6% by weight, more preferably 0.1 to 5% by weight.
- moulded article which is producible from the above-described moulding composition.
- Such moulded article is preferably a lamp housing, lamp extension, lamp reflector, lamp socket, more preferably a lamp plug socket.
- the components a) to d) were compounded on typical compounding machines, e.g. single- or twin-screw extruders or screw kneaders.
- the dried component a) will be metered via a gravimetric metering scale into the intake.
- Component b) can be metered via a gravimetric metering scale into the intake or via a side feeder into the molten component a).
- Components c) and if necessary d) can be metered separately into the intake or via a side feeder into the molten component a).
- Components a), c) and d) can also be metered into the intake in form of dry blends.
- the desired components are mixed and this mixture is homogenized for 10 to 40 min. by means of a tumble mixer, drum hoop mixer, or tumble dryer. To avoid moisture absorption, this can be performed under dry protective gas.
- the compounding is performed at set cylinder temperatures of 70 to 100° C. for the first cylinder and depending on the nature of component a) 310 to 390° C. (respectively 260 to 280° C. for comparison examples 5 and 6) for the remaining cylinders. Vacuum can be applied or degassing can be performed to the atmosphere before the nozzle.
- the melt is extruded in strand form, cooled down in a water bath at 10 to 90° C. and subsequently pelletized. The pellets are dried for 12 to 24 hours at 80 to 120° C. under nitrogen or in vacuum to a water content of less than 0.1 wt-%.
- DSC Differential scanning calometry
- the laser measurements are implemented according to the principle of laser diffraction with a Granulometer Cilas 1064 of Quantachrome GmbH (Germany).
- Fogging is indicated as haze in % calculated by subtraction of haze value of initial glass plate from haze value of glass plate after fogging test.
- Haze measurement is performed according ASTM D 1003 at 23° C. Measuring device: Haze Gard Plus from Byk Gardener with CIE light type C. The haze value is stated in percent of irradiated light quantity.
- test pieces for the flexural modulus and HDT test were produced on an injection moulding machine by the Arburg Company, Modell Allrounder 420 C 1000-250.
- polyamide 6T/6I compounds or polyamide 6T/66 compounds increasing cylinder temperatures from 310° C. to 340° C. were thereby used.
- the moulding temperature was 130 to 150° C.
- polyamide 66 compounds or polyamide 6 compounds increasing cylinder temperatures from 260° C. to 290° C. were thereby used.
- the moulding temperature was 70 to 90° C.
- test bodies were used in a dry state, they were stored for this purpose after the injection moulding for at least 48 h at room temperature in a dry environment, i.e. over silica gel.
- PA 6I/6T polyamide 6T/6I (70/30 mol-%) made of — EMS-CHEMIE AG, hexamethylendiamine, terephthalic acid Switzerland and isophthalic acid RV* 1.56, melting point 325° C.
- PA 6T/66 polyamide 6T/66 (52/48 mol-%) made of — EMS-CHEMIE AG, hexamethylendiamine, terephthalic acid Switzerland and isophthalic acid RV* 1.72, melting point 310° C.
- PA 6 polyamide 6 made of ⁇ -caproclactam 1013B Ube Industries, Japan RV** 2.5, melting point 222° C.
- PA 66 polyamide 66 made of Leona 1200 Asahi Chemical Industry, hexamethylendiamine and adipic acid Japan RV** 2.6, melting point 260° C. Cul copper (I) iodide, purity at least 98%, — Junsei Chemical Co., Ltd, CAS-No. 7681-65-4 Japan KI potassium iodide, purity at least 98%, — Junsei Chemical Co., Ltd, CAS-No.
- the dried pellets of the partially crystalline polyamide 6T/6I (component a)) and a dry blend of components c) and d) were metered separately via gravimetric metering scales into the intake.
- Component b) was metered via a side feeder 4 cylinders Credit the die into the melt.
- the compounding is performed on a twin-screw extruder from Toshiba Machine Co., Ltd. Modell TEM-37BS at a set cylinder temperature of 80° C. for the first cylinder and 325 to 340° C. for the remaining cylinders. Degassing was performed to the atmosphere before the nozzle. The revolution speed was 120 rpm and the throughput 10 kg/h. The strands were cooled down in a water bath at 85° C. and subsequently pelletized. The pellets were dried for 24 hours at 110° C. in vacuum (30 mbar) to a water content of less than 0.1 wt-%.
- Table 2 shows the results for the mechanical and the fogging properties of the inventive examples together with comparative examples.
- Example 1 differs from example 2 that milled glass fibers instead of wollastonite are used as fillers. The best fogging properties were determined for example 1 with milled glass fibers as filler. Also obvious from the comparative examples 4 to 6 is the importance of the selection of the right partially crystalline polyamide. Despite of the same combination of components b) and c) in same amounts only with a partially crystalline polyamide a) containing exclusively aromatic dicarboxylic acids as dicarboxylic acids the fogging requirements can be fulfilled.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
- The present invention refers to a polyamide moulding composition consisting of the following components:
-
- a) 45 to 75% by weight of at least one partially crystalline polyamide consisting of at least one diamine and at least one aromatic dicarboxylic acid, whereupon the at least one diamine has 4 to 18 carbon atoms and is selected from a group of diamines consisting of linear aliphatic diamines, branched aliphatic diamines and cycloaliphatic diamines,
- b) 5 to 20% by weight of at least one fibrous reinforcing agent,
- c) 10 to 40% by weight of at least one non-sized filler which is different from the fibrous reinforcing agent in b),
- d) 0 to 10% by weight of a at least one additive,
- with the proviso that the component b) and c) add up to 25 to 45% by weight and the entirety of components a) to d) add up to 100% by weight.
- Moreover, the present invention refers to a moulded article producible from this moulding composition.
- Polyamide moulded articles are broadly used in the engineering field, in particular for electronic components as well as components in the automotive field. Due to the demand for moulded articles with a reduced weight but a high mechanical strength these articles are in general reinforced by fillers, in particular fibrous fillers.
- Such polyamides moulded articles are also used for lamp articles, like housings or lamp sockets. These can be used for headlights or rear lamps, in particular in the automotive field. For such articles it is important that they show a minimal fogging also at high temperatures which can occur in the surrounding of the lamp.
- WO 2013/026779 A1 describes polyamide composition for LED applications with improved mechanical properties.
- JP 2009-149763 A describes a low volatility polyamide composition with good mechanical properties and a low fogging. The polyamide moulding composition is preferably based on Nylon 6 and Nylon 66.
- Another polyamide composition with good heat resistance, stability under heating and fogging properties is described in EP 2 687 555 A1.
- It was therefore the object of the present invention to provide polyamide moulding compositions with excellent mechanical properties, in particular with a high deflection temperature under load and showing a reduced fogging at high temperatures.
- This problem is solved by the polyamide moulding composition according to claim 1 as well as the moulded article with the features of claim 14. The further dependent claims show preferred embodiments.
- It is provided a polyamide moulding composition which consists of the following components:
-
- a) 45 to 75% by weight of at least one partially crystalline polyamide consisting of at least one diamine and at least one aromatic dicarboxylic acid, whereupon the at least one diamine has 4 to 18 carbon atoms and is selected from a group of diamines consisting of linear aliphatic diamines, branched aliphatic diamines and cycloaliphatic diamines,
- b) 5 to 20% by weight of at least one fibrous reinforcing agent,
- c) 10 to 40% by weight of at least one non-sized filler which is different from the fibrous reinforcing agent in b),
- d) 0 to 10% by weight of a at least one additive,
- The composition has the proviso that the component b) and c) add up to 25 to 45% by weight and the entirety of components a) to d) add up to 100% by weight.
- The inventive composition is characterized by a very low condensable outgasing (fogging) resulting in a haze of a maximum of 10%. The haze is measured by determining the haze on a glass plate after a thermal treatment of pellets of the polyamide moulding composition at 200° C. for a period of 8 hours.
- In the preferred embodiment, the moulding composition has a deflection temperature under load (HDT (A)) according to ISO 75 of at least 190° C., preferably of at least 200 C, and more preferably of at least 210° C.
- The moulding composition has preferably a condensable outgasing (fogging) resulting in a haze of a maximum of 7%, more preferably of 5%.
- In a further preferred embodiment, the moulding composition comprises the partially crystalline polyamide a) in an amount of 50 to 69.95% by weight, more preferably 53 to 64.9% by weight.
- No aliphatic dicarboxylic acids are present in the partially crystalline polyamide a). No lactams or a,w-amino acids are present in the partially crystalline polyamide a).
- The partially crystalline polyamide a) has a melting point of at least 270° C., preferred of 275 to 350° C., more preferred of 280 to 340° C., most preferred of 280 to 330° C.
- The at least one diamine of the partially crystalline polyamide a) is preferably selected from the group of diamines consisting of 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 3,3′-dimethyl-1,5-pentanediamine 1,6-hexanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylene-diamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine and 1,14-tetradecanediamine and mixtures thereof.
- The at least one aromatic dicarboxylic acid of the partially crystalline polyamide a) is preferably selected from the group of aromatic dicarboxylic acids consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, whereupon the portion of isophthalic acid is at most 25 mol-%, preferably at most 20 mol-%, more preferably at most 16 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- More preferably the at least one aromatic dicarboxylic acid of the partially crystalline polyamide is selected from the group of aromatic dicarboxylic acids consisting of terephthalic acid and isophthalic acid, whereupon the portion of isophthalic acid is at most 25 mol-%, preferably at most 20 mol-%, more preferably at most 16 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- The relative viscosity (measured on a solution made of 0,5 g polyamide in 100 ml m-cresol at 20° C.) of the partially crystalline polyamide a) is 1.40 to 2.0, preferably 1.45 to 1.90, more preferably 1.48 to 1.80.
- So as can be seen from the relative viscosity the partially crystalline polyamide a) clearly is a polymer and is not an oligomer.
- Preferably the partially crystalline polyamide a) is selected from the group of partially crystalline polyamides containing as dicarboxylic acids only aromatic dicarboxylic acids, consisting of polyamides with a 4T-unit, polyamides with a 5T-unit, polyamides with a 6T-unit, polyamides with a 8T-unit, polyamides with a 10T-unit, PA 4T/6T, PA 4T/8T, PA 6T/8T, PA 4T/MPMDT, PA 4T/4I, PA 5T/5I, PA 6T/6I, PA 9T/MODT, PA 9T/9I, PA 10T, PA 10T/6T, PA 10T/6T/10I/6I, PA 12T, PA MPMDT/6T, PA 10T/10I, PA 12T/12I, PA 4T/6T/8T, PA 4T/6T/10T, PA 4T/8T/10T, PA6T/8T/10T, PA 4T/6T/MPMDT and mixtures or blends thereof.
- More preferably the partially crystalline polyamide a) is selected from the group of partially crystalline polyamides consisting of PA 6T/61, PA 9T/MODT, PA 10T, PA 10T/6T, PA 10T/6T/10I/6I, PA 12T, PA MPMDT/6T, PA 10T/10I and mixtures or blends thereof.
- Most preferably the partially crystalline polyamide a) is selected from the group of partially crystalline polyamides consisting of PA 6T/6I, PA 10T/6T, PA 10T/6T/10I/6I and mixtures or blends thereof.
- The partially crystalline polyamide 6T/6I is made from hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of hexamethylenediamine of 50 mol-%, an amount of terephthalic acid of 25 to 40 mol-% and an amount of isophthalic acid of 10 to 25 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- Preferably the partially crystalline polyamide 6T/6I is made from 50 mol-% hexamethylenediamine, 30 to 40 mol-% terephthalic acid and 10 to 20 mol-% isophthalic acid, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- More preferably the partially crystalline polyamide 6T/6I is made from 50 mol-% hexamethylenediamine, 35 mol-% terephthalic acid and 15 mol-% isophthalic acid, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%. The melting point of this partially crystalline polyamide is 325° C.
- The above used description of composition of polyamide 6T/6I with 50 mol-% hexamethylenediamine, 35 mol-% terephthalic acid and 15 mol-% isophthalic acid is equivalent to the description PA 6T/6I (70/30 mol-%).
- The partially crystalline polyamide 10T/6T is made from decanediamine, hexamethylenediamine and terephthalic acid with an amount of decanediamine of 20 to 47.5 mol-%, an amount of hexamethylenediamine of 2.5 to 30 mol-% and an amount of terephthalic acid of 50 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%.
- Preferably the partially crystalline polyamide 10T/6T is made from decanediamine, hexamethylenediamine and terephthalic acid with an amount of decanediamine of 30 to 45 mol-%, an amount of hexamethylenediamine of 5.0 to 20 mol-% and an amount of terephthalic acid of 50 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%.
- More preferably the partially crystalline polyamide 10T/6T is made from decanediamine, hexamethylenediamine and terephthalic acid with an amount of decanediamine of 35 to 42.5 mol-%, an amount of hexamethylenediamine of 7.5 to 15 mol-% and an amount of terephthalic acid of 50 mol-%, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%.
- Most preferably the partially crystalline polyamide 10T/6T is made from 42.5 mol-% decanediamine, 7.5 mol-% hexamethylenediamine and 50 mol-% terephthalic acid, whereas the amounts of the three monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-%. The melting point of this partially crystalline polyamide is 295° C.
- The partially crystalline polyamide 10T/6T/10I/6I, is made from decanediamine, hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of decanediamine of 7.5 to 20 mol-%, an amount of hexamethylenediamine of 30 to 42.5 mol-%, an amount of terephthalic acid of 36 to 49.15 mol-% and an amount of isophthalic acid of 0.85 to 14 mol-%, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- Preferably the partially crystalline polyamide 10T/6T/10I/6I, is made from decanediamine, hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of decanediamine of 12.5 to 20 mol-%, an amount of hexamethylenediamine of 30 to 37.5 mol-%, an amount of terephthalic acid of 37.5 to 47.5 mol-% and an amount of isophthalic acid of 2.5 to 12.5 mol-%, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- More preferably the partially crystalline polyamide 10T/6T/10I/6I, is made from decanediamine, hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of decanediamine of 14 to 19 mol-%, an amount of hexamethylenediamine of 31 to 36 mol-%, an amount of terephthalic acid of 40 to 45 mol-% and an amount of isophthalic acid of 5.0 to 10 mol-%, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
- Most preferably the partially crystalline polyamide 10T/6T/10I/6I, is made from 16.65 mol-% decanediamine, 33.35 mol-% hexamethylenediamine, 43.2 mol-% terephthalic acid and 6.8 mol-% isophthalic acid, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%. The melting point of this partially crystalline polyamide is 318° C.
- It is to be noted that the term “polyamide” is a generic term, which comprises both homopolyamides and copolyamides. The abbreviated polyamide nomenclature conforms to the norm ISO 1874-1:2010. The diamine 2-methyl-1,5-pentanediamine is abbreviated as MPMD. The diamine 2-methyl-1,8-octanediamine is abbreviated as MOD.
- It is further preferred that the at least one fibrous reinforcing agent are selected from glass fibres, preferably chopped glass fibres. The fibres reinforcing agent is preferably comprised in an amount of 5 to 15% by weight, more preferably in an amount of 7 to 12% by weight.
- The chopped glass fibres have a fibre length of 1 to 25 mm, preferably 1.5 to 20 mm, more preferably 2 to 12 mm, most preferably 2.5 to 8 mm. The chopped glass fibres have a diameter of 4 to 20 um, preferably 5 to 15 μm, more preferably 6 to 12 μm.
- Chopped glass fibres with a round, oval, elliptical, angular or rectangular cross-section are used. Preferably the chopped glass fibres have a round cross-section.
- The chopped glass fibres are equipped with a suitable sizing system, e.g. on a silane basis. Glass fibres made of all types of glass, such are as e. g. A-, C-, D-, E-, M-, S-, R-glass or any mixtures thereof, can be used. Glass fibres made of E-glass or glass fibres made of mixtures with E-glass or mixtures with E-glass fibres are preferred.
- The at least one non-sized filler has preferably a needle like or flaky shape. The longest dimension of the non-sized filler particle is at most 2500 μm, preferably at most 700 μm, more preferably 0.1 to 300 um. A longest dimension of the non-sized filler particle of at most 2500 μm is particularly common with filler particles having a flaky shape.
- The non-sized fillers are selected from the group consisting of milled glass fibres, milled carbon fibres, glass flakes, whiskers, wollastonite, mica, phyllosilicates and mixtures thereof. These non-sized fillers are in any case different from the fibres reinforcing agents according to b). The at least one non-sized filler is preferably comprised in an amount of 15 to 35% by weight, more preferably 20 to 33% by weight.
- Preferably the non-sized fillers are selected from the group consisting of milled glass fibres, milled carbon fibres, glass flakes, wollastonite, mica and mixtures thereof. More preferably the non-sized fillers are selected from the group consisting of milled glass fibres, wollastonite, mica and mixtures thereof.
- Mica can be natural mica or synthetic mica, whereas synthetic mica is preferred.
- Whiskers are needle-like mono-crystals from metals, oxides, borides, carbides, nitrides, polytitanates, carbon etc. with mostly polygonal cross section, e. g. potassium titanate-, aluminium oxide-, silicium carbide-whisker. Whiskers can be produced by vapour deposition (VS-mechanism) or deposition from a three-phase-system (VLS-mechanism).
- As phyllosilicates, also named layered silicates, e. g. serpentine, talcum, mica, vermiculite, illite, smectites, montmorillonites, kaolin (also named china clay), bentonites can be used. Preferred as phyllosilicates are mica, montmorillonites and kaolin. More preferred as phyllosilicates are mica and montmorillonites.
- According to a preferred embodiment of the invention the moulding composition comprises 32 to 44% by weight, more preferably 35 to 42% by weight of the components b) and c) in sum.
- It is further preferred that the moulding composition comprises at least one additive which is selected from the group consisting of inorganic stabilisers, organic stabilisers, lubricants, colouring- and marking materials, inorganic pigments, organic pigments, IR absorbers, antistatic agents, antiblocking agents, crystal-growth inhibitors, nucleating agents, condensation catalysts, chain extenders, defoamers, chain-lengthening additives, conductivity additives, carbon black, graphite, carbon nanotubes, mould-release agents, separating agents, flame retardants, non-halogen-containing flame retardants, anti-dripping-agents, impact modifiers, optical brighteners, photochromic additives, metallic pigments, metal-coated particles, or mixtures thereof, preferably inorganic stabilizers as copper and potassium iodide.
- The at least one additive is preferably comprised in an amount of 0.05 to 6% by weight, more preferably 0.1 to 5% by weight.
- Moreover, a moulded article is provided which is producible from the above-described moulding composition. Such moulded article is preferably a lamp housing, lamp extension, lamp reflector, lamp socket, more preferably a lamp plug socket.
- Production of Polyamide Moulding Compositions
- To produce the polyamide moulding composition the components a) to d) were compounded on typical compounding machines, e.g. single- or twin-screw extruders or screw kneaders. The dried component a) will be metered via a gravimetric metering scale into the intake. Component b) can be metered via a gravimetric metering scale into the intake or via a side feeder into the molten component a). Components c) and if necessary d) can be metered separately into the intake or via a side feeder into the molten component a). Components a), c) and d) can also be metered into the intake in form of dry blends.
- For production dry blends the desired components are mixed and this mixture is homogenized for 10 to 40 min. by means of a tumble mixer, drum hoop mixer, or tumble dryer. To avoid moisture absorption, this can be performed under dry protective gas.
- The compounding is performed at set cylinder temperatures of 70 to 100° C. for the first cylinder and depending on the nature of component a) 310 to 390° C. (respectively 260 to 280° C. for comparison examples 5 and 6) for the remaining cylinders. Vacuum can be applied or degassing can be performed to the atmosphere before the nozzle. The melt is extruded in strand form, cooled down in a water bath at 10 to 90° C. and subsequently pelletized. The pellets are dried for 12 to 24 hours at 80 to 120° C. under nitrogen or in vacuum to a water content of less than 0.1 wt-%.
- The present invention is described in more detail by the following examples.
- The following measuring specifications were used to analyse the polyamides and test the polyamide moulding compounds.
- Relative Viscosity (RV):
- ISO 307
- Pellets
- 0.5 g in 100 ml m-cresol for PA 6T/6I, PA 6T/66
- 1.0 g in 100 ml sulfuric acid (96%) for PA 6, PA 66
- Temperature 20° C.
- Calculation of the relative viscosity according to RV=t/t0
- Melting Point:
- ISO 11357
- Pellets
- Differential scanning calometry (DSC) was performed at a heating rate of 20 K/min. For the melting point, the temperature was specified at the peak maximum.
- HDT (Heat Deflection Temperature):
- ISO 75
- ISO test bar, standard: ISO/CD 3167, type B1, 80×10×4 mm
- HDT A load 1.80 MPa
- Flexural Modulus:
- ISO 178
- ISO test bar, standard: ISO/CD 3167, type B1, 80×10×4 mm
- Testing speed 2 mm/min
- Temperature 23° C.
- Particle Size Distribution:
- ISO 13320
- Filler particles
- Temperature 23° C.
- The laser measurements are implemented according to the principle of laser diffraction with a Granulometer Cilas 1064 of Quantachrome GmbH (Germany).
- Fogging:
- 50 g of pellets are placed into a beaker (height 90 mm, inner diameter 86 mm) and a round glass plate (98×4.75 mm) is set on the beaker opening. The beaker is immersed 35 mm into an oil-bath for 8 hours at 200° C. After that the glass plate is removed and cooled for 12 hours at 23° C., 50% relative humidity.
- Fogging is indicated as haze in % calculated by subtraction of haze value of initial glass plate from haze value of glass plate after fogging test.
- Haze measurement is performed according ASTM D 1003 at 23° C. Measuring device: Haze Gard Plus from Byk Gardener with CIE light type C. The haze value is stated in percent of irradiated light quantity.
- Production of Test Pieces
- The test pieces for the flexural modulus and HDT test were produced on an injection moulding machine by the Arburg Company, Modell Allrounder 420 C 1000-250. For polyamide 6T/6I compounds or polyamide 6T/66 compounds increasing cylinder temperatures from 310° C. to 340° C. were thereby used. The moulding temperature was 130 to 150° C. For polyamide 66 compounds or polyamide 6 compounds increasing cylinder temperatures from 260° C. to 290° C. were thereby used. The moulding temperature was 70 to 90° C.
- The test bodies were used in a dry state, they were stored for this purpose after the injection moulding for at least 48 h at room temperature in a dry environment, i.e. over silica gel.
- The following materials were used in the examples and comparative examples which are shown in table 1.
- For the preparation of the polyamide moulding compositions the following materials were used (s. Table 1):
-
TABLE 1 Component Description Trade Name Producer PA 6I/6T polyamide 6T/6I (70/30 mol-%) made of — EMS-CHEMIE AG, hexamethylendiamine, terephthalic acid Switzerland and isophthalic acid RV* 1.56, melting point 325° C. PA 6T/66 polyamide 6T/66 (52/48 mol-%) made of — EMS-CHEMIE AG, hexamethylendiamine, terephthalic acid Switzerland and isophthalic acid RV* 1.72, melting point 310° C. PA 6 polyamide 6 made of ε-caproclactam 1013B Ube Industries, Japan RV** 2.5, melting point 222° C. PA 66 polyamide 66 made of Leona 1200 Asahi Chemical Industry, hexamethylendiamine and adipic acid Japan RV** 2.6, melting point 260° C. Cul copper (I) iodide, purity at least 98%, — Junsei Chemical Co., Ltd, CAS-No. 7681-65-4 Japan KI potassium iodide, purity at least 98%, — Junsei Chemical Co., Ltd, CAS-No. 7681-11-0 Japan chopped glass length 3 mm, diameter 11 μm CS3J-260 Nitto Boseki Co., Ltd., fiber Japan milled glass fiber length 70 μm, diameter 10.5 μm, no sizing PF70E-001 Nitto Boseki Co., Ltd., Japan wollastonite needle shape, aspect ratio 15:1, SH-600 Kinsei Matec Co., Ltd, average (D50) particle size 11 μm, Japan CAS-No. 013983-17-0 RV* relative viscosity, measured on a solution made of 0.5 g polyamide in 100 ml m-cresol at 20° C. RV** relative viscosity, measured on a solution made of 1.0 g polyamide in 100 ml sulfuric acid (96%) at 20° C. - Production of polyamide moulding composition of example 1:
- The dried pellets of the partially crystalline polyamide 6T/6I (component a)) and a dry blend of components c) and d) were metered separately via gravimetric metering scales into the intake. Component b) was metered via a side feeder 4 cylinders bevor the die into the melt.
- The compounding is performed on a twin-screw extruder from Toshiba Machine Co., Ltd. Modell TEM-37BS at a set cylinder temperature of 80° C. for the first cylinder and 325 to 340° C. for the remaining cylinders. Degassing was performed to the atmosphere before the nozzle. The revolution speed was 120 rpm and the throughput 10 kg/h. The strands were cooled down in a water bath at 85° C. and subsequently pelletized. The pellets were dried for 24 hours at 110° C. in vacuum (30 mbar) to a water content of less than 0.1 wt-%.
- Table 2 shows the results for the mechanical and the fogging properties of the inventive examples together with comparative examples.
-
TABLE 2 Examples Comparative Examples Component Unit 1 2 3 4 5 6 polyamide 6T/6I wt.-% 59.87 59.87 69.87 — — — polyamide 6T/66 wt.-% — — — 59.87 — — polyamide 66 wt.-% — — — — 59.87 — polyamide 6 wt.-% — — — — — 59.87 chopped glass fibers wt.-% 10 10 30 10 10 10 milled glass fibers wt.-% 30 — — 30 30 30 wollastonite wt.-% — 30 — — — — Cul wt.-% 0.03 0.03 0.03 0.03 0.03 0.03 KI wt.-% 0.1 0.1 0.1 0.1 0.1 0.1 Tests flexural modulus MPa 9380 9300 10590 8340 7700 8010 HDT A (1.80 MPa) ° C. 232 217 284 263 241 196 Fogging haze % 2.1 4.1 13.8 39.7 35.3 34.2 - It is obvious from Table 2 that the inventive examples 1 and 2 have the lowest haze which means the best fogging properties. Example 1 differs from example 2 that milled glass fibers instead of wollastonite are used as fillers. The best fogging properties were determined for example 1 with milled glass fibers as filler. Also obvious from the comparative examples 4 to 6 is the importance of the selection of the right partially crystalline polyamide. Despite of the same combination of components b) and c) in same amounts only with a partially crystalline polyamide a) containing exclusively aromatic dicarboxylic acids as dicarboxylic acids the fogging requirements can be fulfilled.
Claims (15)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2015/053105 WO2016128067A1 (en) | 2015-02-13 | 2015-02-13 | Polyamide moulding composition and moulded article made from this moulding composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20180022900A1 true US20180022900A1 (en) | 2018-01-25 |
| US10544286B2 US10544286B2 (en) | 2020-01-28 |
Family
ID=52477802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US15/546,373 Active 2035-06-27 US10544286B2 (en) | 2015-02-13 | 2015-02-13 | Polyamide moulding composition and moulded article made from this moulding composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US10544286B2 (en) |
| EP (1) | EP3256516B1 (en) |
| JP (1) | JP6497823B2 (en) |
| KR (1) | KR101988868B1 (en) |
| CN (1) | CN107207854B (en) |
| WO (1) | WO2016128067A1 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10577478B2 (en) | 2016-10-21 | 2020-03-03 | Ems-Patent Ag | Polyamide moulding composition and multi-layered structure made therefrom |
| US10717816B2 (en) | 2017-08-18 | 2020-07-21 | Ems-Patent Ag | Reinforced polyamide molding compounds having low haze and molded bodies therefrom |
| US10767047B2 (en) | 2017-08-18 | 2020-09-08 | Ems-Patent Ag | Reinforced polyamide molding compounds having low haze and molded bodies therefrom |
| US10767048B2 (en) | 2017-08-18 | 2020-09-08 | Ems-Patent Ag | Reinforced polyamide molding compounds having low haze and molded bodies therefrom |
| US10836905B2 (en) | 2017-08-31 | 2020-11-17 | Ems-Patent Ag | Polyamide molding compound having high gloss and high notch impact resistance |
| US10899527B2 (en) | 2015-12-23 | 2021-01-26 | Ems-Patent Ag | Method and container for storage and transport of polyamide granulates and correspondingly stored or transported polyamide granulate and also moulded articles produced therefrom |
| US11274204B2 (en) | 2018-10-09 | 2022-03-15 | Ems-Patent Ag | Impact-modified polyamide moulding compounds |
| US11359091B2 (en) | 2017-12-22 | 2022-06-14 | Ems-Patent Ag | Polyamide molding compound |
| US11453778B2 (en) | 2019-08-09 | 2022-09-27 | Ems-Patent Ag | Polyamide moulding compound and its use and mouldings manufactured from the moulding compound |
| US11466153B2 (en) | 2017-12-22 | 2022-10-11 | Ems-Patent Ag | Polyamide molding compound |
| US11814517B2 (en) * | 2019-04-16 | 2023-11-14 | Ems-Patent Ag | Reinforced thermoplastic moulding composition |
| US11981813B2 (en) | 2019-12-23 | 2024-05-14 | Ems-Chemie Ag | Polyamide molding compounds for hypochlorite-resistant applications |
| US12110392B2 (en) | 2020-12-17 | 2024-10-08 | Ems-Chemie Ag | Filled polyamide moulding compounds, moulded articles produced therefrom, and use of the filled polyamide moulding compounds |
| US12291638B2 (en) | 2020-12-17 | 2025-05-06 | Ems-Chemie Ag | Polyamide compounds, molds produced therefrom and use of the polyamide compounds |
| US12344710B2 (en) | 2019-08-09 | 2025-07-01 | Ems-Patent Ag | Semi-crystalline copolyamides, moulding compounds comprising same and their use, and mouldings manufactured from same |
| US12398269B2 (en) | 2019-12-23 | 2025-08-26 | Ems-Chemie Ag | Method of manufacturing a mold that is resistant to hypochlorite |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207854B (en) | 2015-02-13 | 2020-03-03 | 艾曼斯专利股份公司 | Polyamide moulding composition and moulded parts made therefrom |
| CN109486180A (en) * | 2018-10-25 | 2019-03-19 | 合肥永泰新型建材有限公司 | A kind of high-transparency nylon new material and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030153677A1 (en) * | 2000-05-19 | 2003-08-14 | Holger Warth | Impact-resistance modified polymer compositions |
| US20030162900A1 (en) * | 2002-01-31 | 2003-08-28 | Detlev Joachimi | Impact-resistant modified polyamide molding compositions with higher melt viscosity and improved surface quality |
| US20040034152A1 (en) * | 2002-06-21 | 2004-02-19 | Kuraray Co., Ltd. | Polyamide composition |
| US20040167268A1 (en) * | 2002-11-25 | 2004-08-26 | Marc Vathauer | Impact-strength-modified polymer compositions |
| US20080021143A1 (en) * | 2006-07-11 | 2008-01-24 | Helmut Thullen | Polyamide moulding compound and use thereof |
| US20090062452A1 (en) * | 2007-08-24 | 2009-03-05 | Ems-Patent Ag | High-temperature polyamide molding compounds reinforced with flat glass fibers |
| US20110281990A1 (en) * | 2010-05-17 | 2011-11-17 | Ems-Patent Ag | Polyamide moulding material and use thereof for production of led housing components |
| US20140329944A1 (en) * | 2011-12-23 | 2014-11-06 | Ems-Patent Ag | Polyamide molding material, the use thereof, and molded parts produced therefrom |
| US9012566B2 (en) * | 2010-12-02 | 2015-04-21 | Ems-Patent Ag | Polyamide moulding compositions based on mixtures made of transparent copolyamides and of aliphatic homopolyamides for producing transparent mouldings |
| US20170051127A1 (en) * | 2015-08-21 | 2017-02-23 | Lanxess Deutschland Gmbh | Polyamide compositions |
| US20180155510A1 (en) * | 2015-04-22 | 2018-06-07 | Ineos Styrolution Group Gmbh | Method for producing a fibre-composite made from amorphous, chemically modified polymers with reinforcement fibres |
| US10246587B2 (en) * | 2014-03-04 | 2019-04-02 | Arkema France | Transparent polyamide-based composition comprising glass as filler |
| US20190160373A1 (en) * | 2017-11-29 | 2019-05-30 | Alexander Near | Recreational Game Apparatus |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04277553A (en) * | 1991-03-04 | 1992-10-02 | Nippon Steel Chem Co Ltd | Reinforced polyamide resin composition |
| JPH06172643A (en) * | 1992-12-10 | 1994-06-21 | Calp Corp | Complex resin composition |
| JP2002060619A (en) * | 2000-08-22 | 2002-02-26 | Mitsui Chemicals Inc | Thermoplastic, aromatic-containing polyamide resin composition |
| JP2006002113A (en) * | 2004-06-21 | 2006-01-05 | Kuraray Co Ltd | Polyamide resin composition and molded product thereof |
| DE502005001079D1 (en) * | 2005-11-18 | 2007-08-30 | Ems Chemie Ag | Reinforced polyamide molding compounds |
| ATE441684T1 (en) | 2006-03-08 | 2009-09-15 | Basf Se | PARTIALLY AROMATIC COPOLYAMIDES WITH HIGH CRYSTALLINITY |
| WO2008006443A1 (en) * | 2006-07-11 | 2008-01-17 | Dsm Ip Assets B.V. | Lamp sockets |
| JP5451970B2 (en) * | 2006-11-01 | 2014-03-26 | 三菱エンジニアリングプラスチックス株式会社 | Polyamide resin composition pellet blend, molded article, and method for producing pellet blend |
| US9090750B2 (en) | 2007-07-23 | 2015-07-28 | Dsm Ip Assets B.V. | Plastic component for a lighting systems |
| EP2055743B2 (en) * | 2007-10-30 | 2019-03-20 | Ems-Patent Ag | Moulding masses for manufacturing moulded parts in the drinking water sector |
| JP5113506B2 (en) | 2007-12-20 | 2013-01-09 | ユニチカ株式会社 | Low volatility polyamide resin composition |
| EP2354176B1 (en) | 2010-01-28 | 2017-11-15 | Ems-Patent Ag | Partially aromatic moulding masses and their applications |
| JP5942229B2 (en) | 2011-03-15 | 2016-06-29 | 旭化成株式会社 | Polyamide and polyamide composition |
| WO2013026779A1 (en) | 2011-08-19 | 2013-02-28 | Solvay Specialty Polymers Usa, Llc | Improved polyamide compositions for led applications |
| JP6046958B2 (en) | 2011-09-08 | 2016-12-21 | ユニチカ株式会社 | Polyamide resin composition and molded article comprising the same |
| JP2013057003A (en) * | 2011-09-08 | 2013-03-28 | Unitika Ltd | Polyamide resin composition and molding by molding the same |
| CN107207854B (en) | 2015-02-13 | 2020-03-03 | 艾曼斯专利股份公司 | Polyamide moulding composition and moulded parts made therefrom |
-
2015
- 2015-02-13 CN CN201580075696.7A patent/CN107207854B/en active Active
- 2015-02-13 US US15/546,373 patent/US10544286B2/en active Active
- 2015-02-13 WO PCT/EP2015/053105 patent/WO2016128067A1/en not_active Ceased
- 2015-02-13 EP EP15705011.3A patent/EP3256516B1/en active Active
- 2015-02-13 KR KR1020177024413A patent/KR101988868B1/en active Active
- 2015-02-13 JP JP2017536573A patent/JP6497823B2/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030153677A1 (en) * | 2000-05-19 | 2003-08-14 | Holger Warth | Impact-resistance modified polymer compositions |
| US20030162900A1 (en) * | 2002-01-31 | 2003-08-28 | Detlev Joachimi | Impact-resistant modified polyamide molding compositions with higher melt viscosity and improved surface quality |
| US20040034152A1 (en) * | 2002-06-21 | 2004-02-19 | Kuraray Co., Ltd. | Polyamide composition |
| US20040167268A1 (en) * | 2002-11-25 | 2004-08-26 | Marc Vathauer | Impact-strength-modified polymer compositions |
| US20080021143A1 (en) * | 2006-07-11 | 2008-01-24 | Helmut Thullen | Polyamide moulding compound and use thereof |
| US20090062452A1 (en) * | 2007-08-24 | 2009-03-05 | Ems-Patent Ag | High-temperature polyamide molding compounds reinforced with flat glass fibers |
| US20110281990A1 (en) * | 2010-05-17 | 2011-11-17 | Ems-Patent Ag | Polyamide moulding material and use thereof for production of led housing components |
| US9012566B2 (en) * | 2010-12-02 | 2015-04-21 | Ems-Patent Ag | Polyamide moulding compositions based on mixtures made of transparent copolyamides and of aliphatic homopolyamides for producing transparent mouldings |
| US20140329944A1 (en) * | 2011-12-23 | 2014-11-06 | Ems-Patent Ag | Polyamide molding material, the use thereof, and molded parts produced therefrom |
| US10246587B2 (en) * | 2014-03-04 | 2019-04-02 | Arkema France | Transparent polyamide-based composition comprising glass as filler |
| US20180155510A1 (en) * | 2015-04-22 | 2018-06-07 | Ineos Styrolution Group Gmbh | Method for producing a fibre-composite made from amorphous, chemically modified polymers with reinforcement fibres |
| US20170051127A1 (en) * | 2015-08-21 | 2017-02-23 | Lanxess Deutschland Gmbh | Polyamide compositions |
| US20190160373A1 (en) * | 2017-11-29 | 2019-05-30 | Alexander Near | Recreational Game Apparatus |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10899527B2 (en) | 2015-12-23 | 2021-01-26 | Ems-Patent Ag | Method and container for storage and transport of polyamide granulates and correspondingly stored or transported polyamide granulate and also moulded articles produced therefrom |
| US10577478B2 (en) | 2016-10-21 | 2020-03-03 | Ems-Patent Ag | Polyamide moulding composition and multi-layered structure made therefrom |
| US10717816B2 (en) | 2017-08-18 | 2020-07-21 | Ems-Patent Ag | Reinforced polyamide molding compounds having low haze and molded bodies therefrom |
| US10767047B2 (en) | 2017-08-18 | 2020-09-08 | Ems-Patent Ag | Reinforced polyamide molding compounds having low haze and molded bodies therefrom |
| US10767048B2 (en) | 2017-08-18 | 2020-09-08 | Ems-Patent Ag | Reinforced polyamide molding compounds having low haze and molded bodies therefrom |
| US10836905B2 (en) | 2017-08-31 | 2020-11-17 | Ems-Patent Ag | Polyamide molding compound having high gloss and high notch impact resistance |
| US11359091B2 (en) | 2017-12-22 | 2022-06-14 | Ems-Patent Ag | Polyamide molding compound |
| US11466153B2 (en) | 2017-12-22 | 2022-10-11 | Ems-Patent Ag | Polyamide molding compound |
| US11274204B2 (en) | 2018-10-09 | 2022-03-15 | Ems-Patent Ag | Impact-modified polyamide moulding compounds |
| US11814517B2 (en) * | 2019-04-16 | 2023-11-14 | Ems-Patent Ag | Reinforced thermoplastic moulding composition |
| US11453778B2 (en) | 2019-08-09 | 2022-09-27 | Ems-Patent Ag | Polyamide moulding compound and its use and mouldings manufactured from the moulding compound |
| US12344710B2 (en) | 2019-08-09 | 2025-07-01 | Ems-Patent Ag | Semi-crystalline copolyamides, moulding compounds comprising same and their use, and mouldings manufactured from same |
| US11981813B2 (en) | 2019-12-23 | 2024-05-14 | Ems-Chemie Ag | Polyamide molding compounds for hypochlorite-resistant applications |
| US12398269B2 (en) | 2019-12-23 | 2025-08-26 | Ems-Chemie Ag | Method of manufacturing a mold that is resistant to hypochlorite |
| US12110392B2 (en) | 2020-12-17 | 2024-10-08 | Ems-Chemie Ag | Filled polyamide moulding compounds, moulded articles produced therefrom, and use of the filled polyamide moulding compounds |
| US12291638B2 (en) | 2020-12-17 | 2025-05-06 | Ems-Chemie Ag | Polyamide compounds, molds produced therefrom and use of the polyamide compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3256516A1 (en) | 2017-12-20 |
| JP2018505270A (en) | 2018-02-22 |
| JP6497823B2 (en) | 2019-04-10 |
| US10544286B2 (en) | 2020-01-28 |
| KR101988868B1 (en) | 2019-06-13 |
| KR20170109653A (en) | 2017-09-29 |
| EP3256516B1 (en) | 2019-12-25 |
| CN107207854B (en) | 2020-03-03 |
| CN107207854A (en) | 2017-09-26 |
| WO2016128067A1 (en) | 2016-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10544286B2 (en) | Polyamide moulding composition and moulded article made from this moulding composition | |
| KR101721465B1 (en) | Flame-protected, partially aromatic polyamide molding compounds | |
| US10233326B2 (en) | Polyamide moulding compound, moulded article produced herefrom and also purposes of use | |
| JP5198893B2 (en) | Filled polyamide molding material showing reduced water absorption (Detailed description of the invention) | |
| US9815967B2 (en) | Long-fibre-reinforced polyamides | |
| JP5999388B2 (en) | Flame retardant semi-aromatic polyamide composition and molded article produced using the same | |
| US9963591B2 (en) | Polyamide molding material and moldings manufactured from same | |
| JP5335208B2 (en) | Polyamide molding composition and use thereof | |
| US20100279111A1 (en) | Filled polyamide molding materials | |
| US20090280311A1 (en) | Polyamide resin composition and molded article | |
| KR20100098370A (en) | Filled Polyamide Molding Compound | |
| US12110392B2 (en) | Filled polyamide moulding compounds, moulded articles produced therefrom, and use of the filled polyamide moulding compounds | |
| EP2871201A1 (en) | Polyamide, polyamide composition, and molded article | |
| CN103936978A (en) | Polyamide resin and polyamide composition composed of polyamide resin | |
| JP2004059638A (en) | Polyamide composition | |
| JP2015129243A (en) | Polyamide composition and molded product | |
| CN114555712B (en) | Semi-aromatic polyamide mixture and molded article having improved weld line strength | |
| CN112745671A (en) | Polyamide composition with good appearance and high modulus as well as preparation method and application thereof | |
| JP4159788B2 (en) | Polyamide resin composition | |
| WO2025074767A1 (en) | Resin composition, pellet, and molded article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: EMS-PATENT AG, SWITZERLAND Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NAKANO, KOSUKE;ENDO, MAKOTO;HATTA, MINORU;REEL/FRAME:043099/0717 Effective date: 20170723 |
|
| STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
| STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
| STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
| STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
| STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT RECEIVED |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |